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United States Patent |
5,350,859
|
Tanabe
,   et al.
|
September 27, 1994
|
Process for producing 3-hydroxymethyl-1-propargylimidazolidine-2,4-dione
Abstract
Disclosed is a process for producing
3-hydroxymethyl-1-propargylimidazolidine-2,4-dione which comprises
(i) reacting a compound of the formula (I)
##STR1##
wherein R represents an alkyl, alkoxyalkyl or aralkyl group with a
compound of the formula (II)
CH.ident.C--CH.sub.2 --X (II)
wherein X represents a leaving group in the presence of a base to give a
1-propargylimidazolidine-2,4-dione derivative of the formula (III)
##STR2##
wherein R is as defined above and (ii) hydrolyzing this derivative of the
formula (III).
Inventors:
|
Tanabe; Yoo (Nishinomiya, JP);
Murakami; Masanari (Nishinomiya, JP);
Yamamoto; Hitomi (Osaka, JP)
|
Assignee:
|
Sumotomo Chemical Company, Ltd. (Osaka, JP)
|
Appl. No.:
|
020739 |
Filed:
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February 22, 1993 |
Foreign Application Priority Data
Current U.S. Class: |
548/319.1 |
Intern'l Class: |
C07D 233/74 |
Field of Search: |
548/319.1
|
References Cited
U.S. Patent Documents
4176189 | Nov., 1979 | Itaya et al. | 424/273.
|
4200758 | Apr., 1980 | Henrick et al. | 548/312.
|
Foreign Patent Documents |
285270 | Oct., 1988 | EP.
| |
2095675 | Oct., 1982 | GB.
| |
2118182 | Oct., 1983 | GB.
| |
Other References
Orazi et al, New Route for 1-Substituted Hydantions.sup.1, Experientia
XXI/9, Apr. 2, 1965, p. 508.
|
Primary Examiner: Morris; Patricia L.
Attorney, Agent or Firm: Cushman, Darby & Cushman
Claims
What is claimed is:
1. A process for producing 3-hydroxymethyl-1-propargylimidazolidine
-2,4-dione which comprises:
(i) reacting a compound of the formula (I)
##STR6##
wherein R represents an alkyl, alkoxyalkyl or aralkyl group with a
compound of the formula (II)
CH.ident.C--CH.sub.2 --X (II)
wherein X represents a halogen atom or sulfonic acid residue in the
presence of a base to give a 1-propargylimidazolidine -2,4-dione
derivative of the formula (III)
##STR7##
wherein R is as defined above, and (ii) hydrolyzing this derivative of
the formula (III).
2. A process according to claim 1, wherein the hydrolysis in step (ii) is
carried out in an aqueous solution of an acid.
3. A process according to claim 1, wherein the base is alkali metal
hydroxides or alkali metal carbonates.
4. A process according to claim 1, wherein the reaction of step (i) is
carried out in the presence of a phase transfer catalyst.
5. A process according to claim 1, wherein the compound of the formula (II)
and said base are used in an amount of about 1 to about 5 moles and about
1 to about 2 moles, respectively, per mole of the compound of the formula
(I).
6. A process according to claim 1, wherein the reaction in step (i) is
carried out at a temperature within the range of about -10.degree. to
about 50.degree. C. and the hydrolysis in step (ii) is carried out at a
temperature within the range of about 20.degree. to about 100.degree. C.
7. A process for producing
3-hydroxymethyl-1-propargylimidazolidine-2,4-dione which comprises:
(i) reacting imidazolidine-2,4-dione with a compound of the formula (IV)
Y--CH.sub.2 OR (IV)
wherein R represents an alkyl group, an alkoxyalkyl group or an aralkyl
group and Y represents a halogen atom to obtain a compound of the formula
(I):
##STR8##
wherein R represents an alkyl, alkoxyalkyl or aralkyl group, (ii)
reacting a compound of the formula (I) with a compound of the formula (II)
CH.ident.C--CH.sub.2 --X (II)
wherein X represents a halogen atom or sulfonic acid residue in the
presence of a base to give a 1-propargylimidazolidine-2,4-dione derivative
of the formula (III)
##STR9##
wherein R is as defined above, and (iii) hydrolyzing this derivative of
the formula (III).
8. A process according to claim 1, wherein the halogen atom is chlorine,
bromine or iodine and the sulfonic acid residue is --OSO.sub.2 R.sup.A
wherein R.sup.A is C.sub.1 to C.sub.4 alkyl, phenyl or tolyl.
9. A process according to claim 7 wherein the halogen atom is chlorine,
bromine, or iodine.
10. A process for producing 3-hydroxymethyl-1-propargylimidazolidine
-2,4-dione according to claim 1, wherein R represents (C.sub.1 -C.sub.4)
alkyl, (C.sub.1 -C.sub.4) alkoxy (C.sub.1 -C.sub.4) alkyl, or phenyl
substituted (C.sub.1 -C.sub.4) alkyl.
11. A process for producing 3-hydroxymethyl-1-propargylimidazolidine
-2,4-dione according to claim 7, wherein R represents (C.sub.1 -C.sub.4)
alkyl, (C.sub.1 -C.sub.4) alkoxy (C.sub.1 -C.sub.4) alkyl, or phenyl
substituted (C.sub.1 -C.sub.4) alkyl.
Description
The present invention relates to a process for producing
3-hydroxymethyl-1-propargylimidazolidine-2,4dione which is useful as an
intermediate for the production of insecticides.
Since it is known that 3-hydroxymethyl-1-propargylimidazolidine-2,4-dione
represented by the formula
##STR3##
is a useful intermediate for the production of insecticidally active
compounds described in U. S. Pat. No. 4,176,189, development of a
commercially advantageous process for its production has been much
awaited.
We made intensive investigations in an attempt to develop a process for
producing 3-hydroxymethyl-1-propargylimidazolidine-2,4-dione. As a result,
we found that the object can be easily achieved when the process mentioned
below is used. Based on this finding, we have completed the present
invention.
The present invention thus provides a process for producing
3-hydroxymethyl-1-propargylimidazolidine-2,4-dione which comprises
(i) reacting a compound of the formula (I)
##STR4##
wherein R represents an alkyl, alkoxyalkyl or aralkyl group with a
compound of the formula (II)
CH.ident.C--CH.sub.2 --X (II)
wherein X represents a leaving group in the presence of a base to give a
1-proparqylimidazolidine-2,4-dione derivative of the formula (III)
##STR5##
wherein R is as defined above and (ii) hydrolyzing this derivative of the
formula (III).
Referring, first, to R in the above formulas (I) and (III), the alkyl group
includes lower (e.g. C.sub.1 to C.sub.4) alkyl groups such as methyl,
ethyl, etc.; the alkoxyalkyl group includes lower (e.g. C.sub.1 to
C.sub.4) alkoxy-lower (e.g. C.sub.1 to C.sub.4) alkyl groups such as
methoxyethyl, ethoxyethyl, etc.; and the aralkyl group includes
phenyl-substituted lower (e.g. C.sub.1 to C.sub.4) alkyl groups such as
benzyl, .beta.-phenethyl, .alpha.-phenethyl and so on.
The leaving group X in the formula (II) includes halogen atoms such as
chlorine, bromine, iodine, etc. and sulfonic acid residues of the formula
--OSO.sub.2 R.sup.a wherein R.sup.a is a lower (e.g. C.sub.1 -C.sub.4)
alkyl group, a phenyl group, a tolyl group or the like. Examples of such
sulfonic acid residue are methanesulfonic acid residue, p-toluenesulfonic
acid residue, benzenesulfonic acid residue and so on.
The base which is used in the step (i) comprising reacting a compound of
the formula (I) and a compound of the formula (II) includes alkali metal
hydroxides such as potassium hydroxide, sodium hydroxide, etc. and alkali
metal carbonates such as sodium carbonate, potassium carbonate and so on.
The reaction between the compound of the formula (I) and the compound of
the formula (II) in the step (i) is generally conducted in a solvent,
which may for example be selected from among ketones such as methyl
isobutyl ketone, acetone, etc., ethers such as tetrahydrofuran etc.,
halogenated alkanes such as methylene chloride, 1,2-dichloroethane, etc.,
dimethylformamide and dimethyl sulfoxide.
This reaction is generally carried out at a temperature within the range of
usually about -10.degree. C. to about 50.degree. C. for about 1 to about
24 hours. As for the amounts of the reactants, the compound of the formula
(II) is used generally in an amount of about 1 to about 5 moles and the
base is used generally in an amount of about 1 to about 2 moles, each per
mole of the compound of the formula (I).
After completion of the reaction, 1-propargylimidazolidine-2,4-dione
derivative of the formula (III) can be isolated by a conventional
procedure, for example by adding water to the reaction mixture, extracting
it with an organic solvent and removing the solvent under reduced
pressure.
Preferably, this reaction in the step (i) is conducted in the presence of
an auxiliary agent such as a phase transfer catalyst. Such an auxiliary
agent is used generally in an amount of about 0.001 to about 0.2 mole per
mole of the compound of the formula (I). The auxiliary agent mentioned
above includes, among others, tertiary amines such as
tris[2-(2-methoxyethoxy)ethyl]-amine, tris(3,6-dioxaheptyl)amine,
tris(3,6-dioxaoctyl)-amine, etc., quaternary ammonium salts such as
tetra-n-butylammonium bromide, benzyltriethylammonium chloride,
tetra-n-butylammonium sulfate, etc., crown ethers such as 18-crown-6,
dicyclohexano-18-crown-6, etc., and poly-ethylene glycols such as
polyethylene glycol (PEG) 400, PEG 1540, etc. These agents can be used
either singly or in combination.
The resulting 1-propargylimidazolidine-2,4-dione derivative of the formula
(III), either as it is in the crude form or after isolation by
chromatography or the like, is subjected to the step (ii), i.e,,
hydrolysis to give 3-hydroxymethyl-l-propargylimidazolidine-2,4dione.
This hydrolysis reaction in the step (ii) can be carried out by treating
the 1-propargylimidazolidine2,4-dione derivative of the formula (III) in
an aqueous solution of an acid, such as hydrochloric acid or sulfuric
acid, at a temperature in the range of about 20 to about 100.degree. C.
for about 5 minutes to about 24 hours. The amount of said acid is
preferably about 1 to about 500 moles per mole of the
1-propargylimidazolidine-2, 4-dione derivative of a formula (III). After
completion of hydrolysis,
3-hydroxymethyl-1-propargylimidazolidine-2,4-dione can be isolated by a
conventional procedure, for example by removing the solvent under reduced
pressure or diluting the reaction mixture with water and extracting it
with an organic solvent. If necessary, the product compound may be further
subjected to chromatography or the like.
The compound of the formula (I) for use in the present invention can be
prepared by reacting imidazo-lidine-2,4-dione, which is readily available,
with a compound of the formula (IV)
Y--CH.sub.2 OR
wherein R is as defined hereinbefore and Y means a leaving group in the
presence of a base.
Referring to the compound of the formula (IV), the leaving group Y includes
halogens such as chlorine, bromine, iodine. The base for this reaction
includes alkali metal hydroxides such as potassium hydroxide, sodium
hydroxide, etc. and alkali metal carbonates such as sodium carbonate,
potassium carbonate and so on.
The reaction between imidazolidine-2,4-dione and a compound of the formula
(IV) is generally conducted in a solvent. The solvent which can be used
includes ketones such as methyl isobutyl ketone, acetone, etc., ethers
such as tetrahydrofuran etc., halogenated alkanes such as methylene
chloride, 1,2-dichloroethane, etc., dimethylformamide, dimethyl sulfoxide
and so on.
The reaction temperature is generally in the range of about -10 to about
50.degree. C. and the reaction time is generally about 1 to about 24
hours. Per mole of imidazolidine-2,4-dione, compound of the formula (IV)
is used generally in an amount of about 0.3 to about 3 moles and said base
is used generally in an amount of about 0.3 to about 3 moles.
After completion of the reaction, the compound of the formula (I) can be
isolated by a conventional procedure, for example by diluting the reaction
mixture with water, extracting it with an organic solvent and removing the
solvent under reduced pressure.
This reaction is preferably carried out in the presence of an auxiliary
agent such as a phase transfer catalyst. The auxiliary agent is used
generally in an amount of about 0.001 to about 0.2 moles per mole of
imidazolidine-2,4-dione- The auxiliary agent which can be used includes
those mentioned for the reaction between compound (I) and compound (II) in
the step (i).
As described above, the compound of the formula (III) is useful as an
intermediate for preparing the
3-hydroxymethyl-1-propargylimidazolidine-2,4-dione- It is advantageous in
that 3-hydroxymethyl-l-propargyl-imidazolidine-2,4-dione which is a direct
intermediate for the production of the active ingredient of insecticides
can be produced from the compound of the formula (III) by a simple step,
hydrolysis.
The following examples are only intended to describe the present invention
in further detail and should by no means be construed as defining the
scope of the invention.
Example 1-1
In 8 ml of methyl isobutyl ketone were dissolved 500 mg (2.27 mmoles) of
3-benzyloxymethyl-imidazolidine-2,4-dione and 37 mg (0.115 mmoles) of
tetrabutylammonium bromide followed by addition of 114 mg (2.85 mmoles) of
sodium hydroxide at room temperature with stirring. Thereafter, 610 mg
(4.55 mmoles) of propargyl methanesulfonate was added dropwise at room
temperature with stirring and the mixture was further stirred at room
temperature for 7 hours. Water was added to the reaction mixture, and the
mixture was extracted with ethyl acetate. The organic layer was washed
with water and saturated aqueous sodium chloride solution in that order,
and dried over anhydrous sodium sulfate. The solvent was distilled off
under reduced pressure and the residue was subjected to silica gel column
chromatography (eluent; hexane:ethyl acetate =3:1) to give 461 mg (1.78
mmoles) of 3-benzyloxymethyl-l-propargylimidazolidine-2,4-dione.
Yield 79%
.sup.1 H-NMR, .delta.(CDCl.sub.3):2:35 (1H, t, J=2 Hz), 3.90 (2H, s), 4.20
(2H, d, J=2 Hz) 4.65 (2H, s), 5.05 (2H, s), 7.20-7.45 (5H,m)
Example 1-2
To 0.55 g (2.13 mmoles) of
3-benzyloxymethyl-1-propargylimidazolidine-2,4-dione was added 25 ml (304
mmoles) of concentrated (ca. 36% w/w) hydrochloric acid and the mixture
was stirred at 60.degree. C. for 1 hour. The hydrochloric acid was
distilled off under reduced pressure and the residue was subjected to
silica gel column chromatography (eluent; hexane:2-propanol =3:1) to give
0.20 g (1.19 mmoles) of
3-hydroxymethyl-l-pro-pargylimidazolidine-2,4-dione.
Yield 56%
.sup.1 H-NMR, .delta.(CDCl.sub.3): 2.35 (1H, t, J=2 Hz), 4.05 (2H, s), 4.25
(2H, d, J=2 Hz), 5.05 (2H, s), 5.30 (1H, s, --OH)
The following reference examples pertain to the production of the compound
of the formula (I) to be used in the present invention.
Reference Example 1
In 5 ml of methyl isobutyl ketone were suspended 216 mg (3.85 mmoles) of
potassium hydroxide and 73 mg (0.226 mmoles) of
tris[2-(2-methoxyethoxy)ethyl]-amine followed by addition of 900 mg (8.99
mmoles) of imidazolidine-2,4-dione, and the mixture was stirred at room
temperature for 10 minutes. Then, 704 mg (4.50 mmoles) of benzyloxymethyl
chloride was added dropwise at 0.degree. C. and the mixture was stirred at
room temperature for 3 hours. To this reaction mixture was added water and
the organic layer was separated and washed successively with water and
saturated aqueous sodium chloride solution and dried over anhydrous sodium
sulfate. The solvent was then distilled off under reduced pressure and the
residue was subjected to silica gel chromatography (eluent: hexane:ethyl
acetate =1:1) to give 687 mg (3.12 mmoles) of
3-benzyloxymethylimidazolidine-2,4-dione. Yield 70% (based on
benzyloxymethyl chloride) .sup.1 H-NMR, .delta.(CDCl.sub.3): 3.90 (2H, s),
4.60 (2H, s), 5.05 (2H, s), 6.00-6.20 (1H, brs, -NH), 7.20-7.45 (5H, m)
Reference Example 2
Using 73 mg (0,126 mmoles) of tetrabutyl-ammonium sulfate in lieu of 73 mg
of tris[2-(2-methoxyethoxy)ethyl]amine, the procedure of Reference Example
1 was otherwise repeated to give 612 mg (2.78 mmoles) of
3-benzyloxymethylimidazolidine-2,4-dione. Yield 62% (based on
benzyloxymethyl chloride)
Reference Example 3
Using 73 mg (0.226 mmole) of tetrabutylammonium bromide in lieu of 73 mg of
tris[2-(2-methoxyethoxy)-ethyl]amine, the procedure of Reference Example 1
was otherwise repeated to give 556 mg (2.52 mmoles) of
3-benzyloxymethylimidazolidine-2,4-dione. Yield 56% (based on
benzyloxymethyl chloride)
Reference Example 4
Using 346 mg (0.225 mmole) of polyethylene glycol 1540 in lieu of 73 mg of
tris[2-(2-methoxyethoxy)ethyl]amine, the procedure of Reference Example 1
was otherwise repeated to give 562 mg (2.55 mmoles) of
3-benzyloxymethylimidazolidine-2,4-dione. Yield 57% (based on
benzyloxymethyl chloride)
In accordance with the process of the present invention,
3-hydroxymethyl-1-propargylimidazolidine-2,4-dione, an important
intermediate for the production of insecticidally active compounds, can be
easily produced. Such insecticidally active compounds can be produced from
said 3-hydroxymethyl-1-propargylimidazolidine-2.4-dione by the method
described in U.S. Pat. No. 4,176,189.
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